JP2013060309A - Nanostructured porous body excellent in hydrophobicity - Google Patents
Nanostructured porous body excellent in hydrophobicity Download PDFInfo
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本発明は、疎水性に優れるナノ構造多孔質体に関するもので、発泡剤を使用しない断熱材として経年変化が小さく、耐熱性にも優れることから建築用断熱材を始め、車両用断熱材、電子機器用断熱材に使用できる。また、防寒衣料、防寒靴、防寒寝具などの日用品など幅広い分野で応用できるものである。 The present invention relates to a nanostructured porous body having excellent hydrophobicity, and as a heat insulating material that does not use a foaming agent, the secular change is small and the heat resistance is excellent. Can be used for insulation for equipment. Moreover, it can be applied in a wide range of fields such as daily clothing such as winter clothing, winter shoes, and cold bedding.
シリカ系ナノ構造を有する多孔質体の製造方法は、一般的にゾルーゲル法によって湿潤ゲルを合成し、その後、得られた湿潤ゲルを炭酸ガスの超臨界流体によって乾燥する方法が知られている。 As a method for producing a porous body having a silica-based nanostructure, generally, a wet gel is synthesized by a sol-gel method, and then the obtained wet gel is dried by a supercritical fluid of carbon dioxide gas.
そして、ゾルーゲル法によって合成された湿潤ゲルは、その表面にＯＨ基を持つため親水性であり、その状態で炭酸ガスの超臨界流体乾燥を行ってシリカ系ナノ構造を有する多孔質体を得ると、その得られた多孔質体は吸湿し易く、結果、断熱性能が低下する問題があった。 And the wet gel synthesized by the sol-gel method is hydrophilic because it has OH groups on its surface, and when a porous body having a silica-based nanostructure is obtained by performing supercritical fluid drying of carbon dioxide gas in that state. The obtained porous body is easy to absorb moisture, resulting in a problem that the heat insulating performance is lowered.
そこで、特許文献１に記載されているように、湿潤ゲルの状態でシリカ末端のＯＨ基に疎水化反応をさせることで吸湿し難いシリカ系ナノ構造を有する多孔質体を得る方法が提案されている。 Therefore, as described in Patent Document 1, a method of obtaining a porous body having a silica-based nanostructure that is difficult to absorb moisture by causing a hydrophobic reaction to the OH group at the end of silica in a wet gel state has been proposed. Yes.
しかしながら、特許文献１記載の方法は、ゾルーゲル法によってシリカ系の湿潤ゲルを合成した後、シリカ末端のＯＨ基に疎水化反応をさせるので工程数が増え、効率的ではない。その上、該湿潤ゲル内部まで疎水化することは困難である。 However, the method described in Patent Document 1 is not efficient because the silica-based wet gel is synthesized by the sol-gel method and then the OH group at the end of the silica is subjected to a hydrophobization reaction, thereby increasing the number of steps. Moreover, it is difficult to make the inside of the wet gel hydrophobic.
そこで、ゾルーゲル法によってシリカ系の湿潤ゲルを合成する際に、シリカ末端のＯＨ基に疎水化反応をさせるシラン系表面処理剤を添加する方法を検討した。ところが、この方法を採用すると、シラン系表面処理剤の種類によっては所望の疎水化がされない問題があった。 Therefore, when synthesizing a silica-based wet gel by the sol-gel method, a method of adding a silane-based surface treatment agent that causes a hydrophobic reaction to the OH group at the end of the silica was investigated. However, when this method is employed, there is a problem that the desired hydrophobicity is not achieved depending on the type of the silane surface treatment agent.
本発明は、ゾルーゲル法によってシリカ系の湿潤ゲルを合成する際に、シリカ末端のＯＨ基に疎水化反応をさせるシラン系表面処理剤を添加する方法において、所望の疎水化された湿潤ゲルを得、最終的に疎水性に優れたナノ構造を有する多孔質体を提供することを目的とする。 The present invention provides a desired hydrophobized wet gel in a method of adding a silane surface treatment agent that causes a hydrophobization reaction to the OH group at the end of silica when synthesizing a silica wet gel by the sol-gel method. Finally, an object is to provide a porous body having a nanostructure with excellent hydrophobicity.
本発明は、ゾルーゲル法によってシリカ系の湿潤ゲルを合成する際に、シリカ末端のＯＨ基に疎水化反応をさせる特定のシラン系表面処理剤を特定量添加することで、疎水性に優れた湿潤ゲルを得、最終的に疎水性に優れたナノ構造を有する多孔質体を得られることを見出した。 When synthesizing a silica-based wet gel by the sol-gel method, the present invention adds a specific amount of a specific silane-based surface treatment agent that causes a hydrophobization reaction to the OH group at the end of the silica, so that wetting with excellent hydrophobicity is achieved. It was found that a gel was obtained, and finally a porous body having a nanostructure with excellent hydrophobicity could be obtained.
本発明の請求項１記載の疎水性に優れるナノ構造多孔質体の製造方法は、テトラアルコキシシランにシラン系表面処理剤を添加し、アルカリ触媒下でのゾルーゲル法で湿潤ゲルを得、得られた湿潤ゲルを超臨界炭酸ガス乾燥法によって乾燥して得られるナノ構造多孔質体の製造方法であって、前記シラン系表面処理剤は、Ｓｉ(ＯＣＨ３)ｎＸ４−ｎ(ｎ＝２〜３、Ｘ＝アルキル基)の化学式で表されるものであり、かつ、モル比率でテトラアルコキシシラン／シラン系表面処理剤＝９／１〜２／８の範囲で添加されることを特徴とする。また、請求項１記載の構成に加えて、ゾルーゲル法で湿潤ゲルを合成する際、超音波撹拌を行うことを特徴とする。 The method for producing a porous nanostructure having excellent hydrophobicity according to claim 1 of the present invention is obtained by adding a silane-based surface treatment agent to tetraalkoxysilane and obtaining a wet gel by a sol-gel method under an alkali catalyst. The nano-structure porous body obtained by drying the wet gel by a supercritical carbon dioxide drying method, wherein the silane-based surface treatment agent is Si (OCH 3 ) n X 4-n (n = 2) ~ 3, X = alkyl group) and is added in a molar ratio of tetraalkoxysilane / silane-based surface treatment agent = 9/1 to 2/8. To do. Moreover, in addition to the structure of Claim 1, when synthesize | combining a wet gel with a sol-gel method, ultrasonic stirring is performed.
所望の疎水化された湿潤ゲルを得、最終的に疎水性に優れたナノ構造を有する多孔質体を得ることができる。 A desired hydrophobized wet gel can be obtained, and finally a porous body having a nanostructure with excellent hydrophobicity can be obtained.
本発明は、テトラアルコキシシランにシラン系表面処理剤を添加し、アルカリ触媒下でのゾルーゲル法で湿潤ゲルを得、得られた湿潤ゲルを超臨界炭酸ガス乾燥法によって乾燥して得られるナノ構造多孔質体の製造する方法であって、前記シラン系表面処理剤は、Ｓｉ(ＯＣＨ３)ｎＸ４−ｎ(ｎ＝２〜３、Ｘ＝アルキル基)の化学式で表されるものであり、かつ、モル比率でテトラアルコキシシラン／シラン系表面処理剤＝９／１〜２／８の範囲で添加されることを特徴とする。 The present invention is a nanostructure obtained by adding a silane-based surface treatment agent to tetraalkoxysilane, obtaining a wet gel by a sol-gel method under an alkali catalyst, and drying the obtained wet gel by a supercritical carbon dioxide drying method A method for producing a porous body, wherein the silane-based surface treatment agent is represented by a chemical formula of Si (OCH 3 ) n X 4-n (n = 2 to 3, X = alkyl group). And, it is added in the range of tetraalkoxysilane / silane surface treatment agent = 9/1 to 2/8 in molar ratio.
本発明は、ゾルーゲル法によってシリカ系の湿潤ゲルを合成する際に、特定のシラン系表面処理剤を特定量添加するものであり、シラン系表面処理剤としては、Ｓｉ(ＯＣＨ３)ｎＸ４−ｎ(ｎ＝２〜３、Ｘ＝アルキル基)の化学式で表されるものであり、例えばメチルトリメトキシシラン、ジメチルジメトキシシラン、ヘキシルトリメトキシシラン、デシルトリメトキシシランが挙げられ、更にこれらの縮合体である信越化学工業社製のＫＣ−８９Ｓ、同社製のＫＲ−５００、同社製のＸ−４０−２３０８、エボニック社製のＤｙｎａｓｙｌａｎ９８９６、コルコート社製のＳＳ−１０１が挙げられる。その中でも特に、メチルトリメトキシシラン、ジメチルジメトキシシラン及びそれらの縮合体がテトラアルコキシシランとの相溶性が良好なことから好適に使用される。
なお、メチルトリエトキシシランやジメチルジエトキシシランは、本発明のＳｉ(ＯＣＨ３)ｎＸ４−ｎ(ｎ＝２〜３、Ｘ＝アルキル基)の化学式で表されるシラン系表面処理剤に比べて、反応性が低いため疎水化の効果が得られない。更に、１，１，１，３，３，３−ヘキサメチルジシラザンやトリメチルクロロシランは、テトラアルコキシシランや溶媒と副反応を起こすことから疎水化の効果が得られない。
In the present invention, when a silica-based wet gel is synthesized by a sol-gel method, a specific amount of a specific silane-based surface treatment agent is added. As the silane-based surface treatment agent, Si (OCH 3 ) n X 4 -N (n = 2 to 3, X = alkyl group), and examples thereof include methyltrimethoxysilane, dimethyldimethoxysilane, hexyltrimethoxysilane, and decyltrimethoxysilane. Examples of the condensate include KC-89S manufactured by Shin-Etsu Chemical Co., Ltd., KR-500 manufactured by the same company, X-40-2308 manufactured by the same company, Dynasylan 9896 manufactured by Evonik, and SS-101 manufactured by Colcoat. Among these, methyltrimethoxysilane, dimethyldimethoxysilane and their condensates are particularly preferably used because of their good compatibility with tetraalkoxysilane.
Methyltriethoxysilane and dimethyldiethoxysilane are used as silane-based surface treatment agents represented by the chemical formula of Si (OCH 3 ) n X 4-n (n = 2 to 3, X = alkyl group) of the present invention. In comparison, since the reactivity is low, the effect of hydrophobicity cannot be obtained. Furthermore, 1,1,1,3,3,3-hexamethyldisilazane and trimethylchlorosilane cause a side reaction with tetraalkoxysilane and a solvent, so that the hydrophobizing effect cannot be obtained.
また、本発明シラン系表面処理剤は、モル比率でテトラアルコキシシラン／シラン系表面処理剤＝９／１〜２／８の範囲で添加される。シラン系表面処理剤が所定量よりも少ないと、所望の疎水性が得られない。逆にシラン系表面処理剤が所定量よりも多いと、ゾル−ゲル法により湿潤ゲルを得る際、ゲル化されず、結果、ナノ構造を有する多孔質体が得られない。 Moreover, this invention silane type surface treating agent is added in the range of tetraalkoxysilane / silane type | system | group surface treating agent = 9/1-2/8 by molar ratio. When the amount of the silane surface treatment agent is less than a predetermined amount, desired hydrophobicity cannot be obtained. On the other hand, when the amount of the silane-based surface treatment agent is larger than a predetermined amount, when a wet gel is obtained by the sol-gel method, it is not gelled, and as a result, a porous body having a nanostructure cannot be obtained.
本発明で使用されるテトラアルコキシランは、テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン、テトラブトキシシラン、更にこれらの縮合体であるメチルシリケート、エチルシリケートなどが挙げられ、特にテトラメトキシシランは、シラン系表面処理剤との相溶性が良好なことから好適に使用される。 Examples of the tetraalkoxylane used in the present invention include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and condensates thereof such as methyl silicate and ethyl silicate. It is preferably used because of its good compatibility with silane-based surface treatment agents.
また、本発明のゾルーゲル法では、テトラアルコキシシランとシラン系表面処理剤の他にアルカリ触媒、水、溶媒が使用される。アルカリ触媒としてアンモニア、炭酸水素ナトリウムが挙げられるが、これらはアンモニア水や炭酸水素ナトリウム水溶液として使用される。溶媒としては、炭酸ガスの超臨界流体との相溶性がよいメタノール、エタノールなどのアルコール類が好適に使用される。 In the sol-gel method of the present invention, an alkali catalyst, water, and a solvent are used in addition to the tetraalkoxysilane and the silane surface treatment agent. Examples of the alkali catalyst include ammonia and sodium hydrogen carbonate, which are used as aqueous ammonia and aqueous sodium hydrogen carbonate solution. As the solvent, alcohols such as methanol and ethanol having good compatibility with the supercritical fluid of carbon dioxide are preferably used.
本発明は、ゾルーゲル法で湿潤ゲルを合成する際に超音波撹拌を行うことがよい。具体的には、テトラメトキシシランとシラン系表面処理剤を原料とし、溶媒、アルカリ触媒、水を配合し、超音波攪拌機による撹拌を行って湿潤ゲルを得る方法である。この方法により得られた湿潤ゲルは、バルク状(ブロック状)ではなく、粒子状の湿潤ゲルであるため、その後の炭酸ガスによる超臨界流体で乾燥する際、バルク状の湿潤ゲルを乾燥するよりも早く、湿潤ゲル中に含まれる溶媒を取り除くことができる。更に、乾燥して得られた粒子状のナノ構造を有する多孔質体は、粉砕工程が不要であり、粉砕時の粉体飛散の問題がなく、しかも工程数を減らすことができるので効率的である。 In the present invention, ultrasonic stirring is preferably performed when a wet gel is synthesized by a sol-gel method. Specifically, this is a method in which tetramethoxysilane and a silane-based surface treatment agent are used as raw materials, a solvent, an alkali catalyst, and water are blended, and a wet gel is obtained by stirring with an ultrasonic stirrer. Since the wet gel obtained by this method is not a bulk (block), but a particulate wet gel, when drying with a supercritical fluid using carbon dioxide gas, the bulk wet gel is dried. As soon as possible, the solvent contained in the wet gel can be removed. Furthermore, the porous body having a particulate nanostructure obtained by drying does not require a pulverization step, and there is no problem of powder scattering during pulverization, and the number of steps can be reduced. is there.
（実施例1）
テトラメトキシシラン（コルコート社製のＴＭＯＳ：メチルシリケート）０．９モルに、シラン系表面処理剤のジメチルジメトキシシラン(信越化学工業社製のＫＢＭ−２２)０．１モルを原料とし、アルカリ触媒のアンモニア０．０１モル、水４．１、メタノール７．２モルを配合し、メカニカルスターラー(ＩＫＡ社製)による撹拌を行い、湿潤ゲルを得た。
続いて、得られた湿潤ゲルをメタノールで洗浄後、圧力容器に入れて超臨界炭酸ガス乾燥（８０℃、２０Ｍｐａ）でメタノール残存量が１００ｐｐｍ以下になるまで８時間乾燥を行い、ナノ構造を有する多孔質体を得た。
(Example 1)
Tetramethoxysilane (Colcoat TMOS: methyl silicate) 0.9 mol, silane-based surface treatment agent dimethyldimethoxysilane (Shin-Etsu Chemical Co., Ltd. KBM-22) 0.1 mol as a raw material, A mixture of 0.01 mol of ammonia, 4.1 mol of water and 7.2 mol of methanol was stirred with a mechanical stirrer (manufactured by IKA) to obtain a wet gel.
Subsequently, the obtained wet gel was washed with methanol, then placed in a pressure vessel, and dried for 8 hours until the residual amount of methanol was 100 ppm or less by supercritical carbon dioxide drying (80 ° C., 20 Mpa) to have a nanostructure. A porous body was obtained.
（実施例２）
テトラメトキシシラン（コルコート社製のＴＭＯＳ：メチルシリケート）０．８モルに、シラン系表面処理剤のジメチルジメトキシシラン(信越化学工業社製のＫＢＭ−２２)０．２モルを原料とした以外は、実施例１同様の方法にて、ナノ構造を有する多孔質体を得た。
(Example 2)
Tetramethoxysilane (Colcoat Co., Ltd. TMOS: methyl silicate) 0.8 mol, except that the silane-based surface treatment agent dimethyldimethoxysilane (Shin-Etsu Chemical Co., Ltd. KBM-22) 0.2 mol was used as a raw material, A porous body having a nanostructure was obtained in the same manner as in Example 1.
（実施例３）
テトラメトキシシラン（コルコート社製のＴＭＯＳ：メチルシリケート）０．８モルに、シラン系表面処理剤のジメチルジメトキシシラン(信越化学工業社製のＫＢＭ−２２)０．２モルを原料とし、アルカリ触媒として炭酸水素ナトリウム、水４．１、メタノール７．２モルを配合し、超音波攪拌機(日本精機製作所社製のＵＳ−３００Ｔ：出力１５０Ｗ、周波数２０ｋＨｚ、)による撹拌を４５分間行い、粒子状湿潤ゲルを得た。
続いて、得られた湿潤ゲルをメタノールで洗浄後、圧力容器に入れて超臨界炭酸ガス乾燥（８０℃、２０Ｍｐａ）でメタノール残存量が１００ｐｐｍ以下になるまで２．５時間乾燥を行い、ナノ構造を有する多孔質体を得た。
なお、得られた多孔質体は、平均粒子径が１０μｍの微粉末である。
(Example 3)
Tetramethoxysilane (Colcoat Co. TMOS: methyl silicate) 0.8 mol, silane-based surface treatment agent dimethyldimethoxysilane (Shin-Etsu Chemical Co., Ltd. KBM-22) 0.2 mol as a raw material, as an alkali catalyst Mixing sodium hydrogen carbonate, water 4.1, and methanol 7.2 mol, stirring with an ultrasonic stirrer (US-300T manufactured by Nippon Seiki Seisakusho Co., Ltd .: output 150 W, frequency 20 kHz) for 45 minutes, particulate wet gel Got.
Subsequently, the wet gel obtained was washed with methanol, placed in a pressure vessel, and dried for 2.5 hours until the residual amount of methanol was 100 ppm or less by drying with supercritical carbon dioxide (80 ° C., 20 Mpa). A porous body having was obtained.
In addition, the obtained porous body is a fine powder with an average particle diameter of 10 μm.
（実施例４）
テトラメトキシシラン（コルコート社製のＴＭＯＳ：メチルシリケート）０．２モルに、シラン系表面処理剤のジメチルジメトキシシラン(信越化学工業社製のＫＢＭ−２２)０．８モルを原料とした以外は、実施例１同様の方法にて、ナノ構造を有する多孔質体を得た。
Example 4
Tetramethoxysilane (Colcoat Co., Ltd. TMOS: methyl silicate) 0.2 mol, except that the silane surface treatment agent dimethyldimethoxysilane (Shin-Etsu Chemical Co., Ltd. KBM-22) 0.8 mol was used as a raw material, A porous body having a nanostructure was obtained in the same manner as in Example 1.
（比較例1）
テトラメトキシシラン（コルコート社製のＴＭＯＳ：メチルシリケート）１モルのみを原料とした以外は、実施例１同様の方法にて、ナノ構造を有する多孔質体を得た。
(Comparative Example 1)
A porous material having a nanostructure was obtained in the same manner as in Example 1 except that only 1 mol of tetramethoxysilane (TMOS: methyl silicate manufactured by Colcoat) was used as a raw material.
（比較例２）
テトラメトキシシラン（コルコート社製のＴＭＯＳ：メチルシリケート）０．９５モルに、シラン系表面処理剤のジメチルジメトキシシラン(信越化学工業社製のＫＢＭ−２２)０．０５モルを原料とした以外は、実施例１同様の方法にて、ナノ構造を有する多孔質体を得た。
(Comparative Example 2)
Except for using 0.95 mol of tetramethoxysilane (TMOS manufactured by Colcoat Co., Ltd.) and 0.05 mol of dimethyldimethoxysilane (KBM-22 manufactured by Shin-Etsu Chemical Co., Ltd.) as a raw material, A porous body having a nanostructure was obtained in the same manner as in Example 1.
（比較例３）
テトラメトキシシラン（コルコート社製のＴＭＯＳ：メチルシリケート）０．９モルに、シラン系表面処理剤のジメチルジエトキシシラン(信越化学工業社製のＫＢＥ−２２)０．１モルを原料とした以外は、実施例１同様の方法にて、ナノ構造を有する多孔質体を得た。
(Comparative Example 3)
Except that 0.9 mol of tetramethoxysilane (TMOS: methyl silicate manufactured by Colcoat Co.) and 0.1 mol of dimethyldiethoxysilane (KBE-22 manufactured by Shin-Etsu Chemical Co., Ltd.) as a raw material were used as raw materials. In the same manner as in Example 1, a porous body having a nanostructure was obtained.
（比較例４）
テトラメトキシシラン（コルコート社製のＴＭＯＳ：メチルシリケート）０．９モルに、シラン系表面処理剤の１，１，１，３，３，３−ヘキサメチルジシラザン(信越化学工業社製のＨＭＤＳ)０．１モルを原料とした以外は、実施例１同様の方法にて、ナノ構造を有する多孔質体を得た。
(Comparative Example 4)
1,1,1,3,3,3-hexamethyldisilazane (HMDS manufactured by Shin-Etsu Chemical Co., Ltd.), a silane-based surface treatment agent, was added to 0.9 mol of tetramethoxysilane (TMOS: methyl silicate manufactured by Colcoat Co.). A porous body having a nanostructure was obtained in the same manner as in Example 1 except that 0.1 mol was used as a raw material.
（比較例５）
テトラメトキシシラン（コルコート社製のＴＭＯＳ：メチルシリケート）０．１モルに、シラン系表面処理剤のジメチルジメトキシシラン(信越化学工業社製のＫＢＭ−２２)０．９モルを原料とし、アルカリ触媒のアンモニア０．０１モル、水４．１、メタノール７．２モルを配合し、メカニカルスターラー(ＩＫＡ社製)による撹拌を行った。しかしながら、ゲル化されず、湿潤ゲルが得られなかった。すなわち、ナノ構造を有する多孔質体が得られなかった。
(Comparative Example 5)
Tetramethoxysilane (Colcoat TMOS: methyl silicate) 0.1 mol, silane-based surface treatment agent dimethyldimethoxysilane (Shin-Etsu Chemical Co., Ltd. KBM-22) 0.9 mol as a raw material, 0.01 mol of ammonia, 4.1 mol of water, and 7.2 mol of methanol were blended, and stirring was performed with a mechanical stirrer (manufactured by IKA). However, it did not gel and a wet gel was not obtained. That is, a porous body having a nanostructure was not obtained.
実施例１ないし４、比較例１ないし４にて得られたナノ構造を有する多孔質体について、ＩＲ分析、浸水試験、熱伝導率、湿熱試験後の熱伝導率を以下の方法にて測定した。結果を表１に示す。なお、比較例５は、ナノ構造を有する多孔質体が得られなかったので測定不能であった。 About the porous body which has a nanostructure obtained in Examples 1 to 4 and Comparative Examples 1 to 4, IR analysis, water immersion test, thermal conductivity, and thermal conductivity after wet heat test were measured by the following methods. . The results are shown in Table 1. Note that Comparative Example 5 was not measurable because a porous body having a nanostructure was not obtained.
（ＩＲ分析）
得られた多孔質体の赤外吸収分析を行ってＯＨ基を示す３４６５ｃｍ−１付近の吸収（ＩＯＨ）と、ＣＨ３基を示す２９８４ｃｍ−１付近の吸収（ＩＣＨ３）の強度比ＩＯＨ／ＩＣＨ３を算出した。結果、その値が１．０未満であれば「疎水性」、１．０以上であれば「親水性」と判断した。
(IR analysis)
The obtained porous body was subjected to infrared absorption analysis, and the intensity ratio I OH between absorption near 3465 cm −1 representing OH groups (I OH ) and absorption near 2984 cm −1 representing CH 3 groups (I CH3 ) / I CH3 was calculated. As a result, when the value was less than 1.0, it was judged as “hydrophobic”, and when it was 1.0 or more, it was judged as “hydrophilic”.
参考迄に実施例１ないし２、比較例１で得られた多孔質体のＩＲ分析による（ＩＯＨ）と（ＩＣＨ３）の吸収量を示すグラフを図１に示す。 For reference, a graph showing absorption amounts of (I OH ) and (I CH 3 ) by IR analysis of the porous bodies obtained in Examples 1 and 2 and Comparative Example 1 is shown in FIG.
（浸水試験）
得られた多孔質体を、室温の水に撹拌しながら浸漬させ、３０分間静置した後の状態を目視にて観察した。結果、多孔質体の粒子が水表面に浮遊している状態を水に「不溶」とし「疎水性」と判断した。また、多孔質体の粒子が水に分散している状態を水に「分散」とし「親水性」と判断した。
(Inundation test)
The obtained porous body was immersed in room temperature water while stirring, and the state after standing for 30 minutes was visually observed. As a result, the state in which the porous particles floated on the water surface was determined to be “insoluble” in water and “hydrophobic”. In addition, the state in which the porous particles were dispersed in water was determined as “dispersed” in water and determined to be “hydrophilic”.
（湿熱試験前の熱伝導率）
実施例１ないし２、及び４、比較例１ないし４で得られた多孔質体をジェットミル粉砕機で粉砕した後、１２０メッシュのふるいにかけて平均粒子径１０μｍの微粉末を得た。なお、実施例３で得られた多孔質体は、既に平均粒子径１０μｍの微粉末であるため、粉砕機による粉砕を省略した。
続いて、得られた多孔質体の微粉末を、ポリエチレン袋に充填して２０ｍｍ厚とし、オートラムダ機（英弘精機社製、ＨＣ−０７４）にて熱伝導率を測定した。
(Thermal conductivity before wet heat test)
The porous bodies obtained in Examples 1 to 2 and 4 and Comparative Examples 1 to 4 were pulverized with a jet mill pulverizer and then passed through a 120 mesh sieve to obtain fine powder having an average particle size of 10 μm. In addition, since the porous body obtained in Example 3 was already a fine powder having an average particle diameter of 10 μm, pulverization by a pulverizer was omitted.
Subsequently, the obtained fine powder of the porous body was filled in a polyethylene bag to a thickness of 20 mm, and the thermal conductivity was measured with an auto lambda machine (HC-074, manufactured by Eihiro Seiki Co., Ltd.).
（湿熱試験後の熱伝導率）
上記方法にて得られた多孔質体の微粉末を、７０℃、９５％ＲＨ条件の恒温槽に１週間保管した後、その多孔質体をポリエチレン袋に充填して２０ｍｍ厚とし、オートラムダ機（英弘精機社製、ＨＣ−０７４）にて熱伝導率を測定した。
(Thermal conductivity after wet heat test)
The porous body fine powder obtained by the above method was stored in a constant temperature bath at 70 ° C. and 95% RH for 1 week, and then the porous body was filled in a polyethylene bag to a thickness of 20 mm. The thermal conductivity was measured with HC-074 (Hideko Seiki Co., Ltd.).
結果、実施例１ないし４で得られた多孔質体は疎水性であるため、湿熱条件下で湿気を吸収することが少なく、湿熱試験前の熱伝導率と湿熱試験後の熱伝導率を比べても変化が少ないものであった。また、比較例１ないし４で得られた多孔質体は親水性であるため、湿熱条件下で湿気を吸収することが大きく、湿熱試験前の熱伝導率と湿熱試験後の熱伝導率を比べると変化が大きいものであった。 As a result, since the porous bodies obtained in Examples 1 to 4 are hydrophobic, they hardly absorb moisture under wet heat conditions, and the thermal conductivity before the wet heat test is compared with the heat conductivity after the wet heat test. But there was little change. Moreover, since the porous body obtained in Comparative Examples 1 to 4 is hydrophilic, it absorbs moisture under wet heat conditions, and the thermal conductivity before the wet heat test is compared with the heat conductivity after the wet heat test. And the change was big.
Claims (2)
前記シラン系表面処理剤は、Ｓｉ(ＯＣＨ３)ｎＸ４−ｎ(ｎ＝２〜３、Ｘ＝アルキル基)の化学式で表されるものであり、かつ、モル比率でテトラアルコキシシラン／シラン系表面処理剤＝９／１〜２／８の範囲で添加されることを特徴とする疎水性に優れるナノ構造多孔質体の製造方法。 A nanostructured porous material obtained by adding a silane surface treatment agent to tetraalkoxysilane, obtaining a wet gel by a sol-gel method under an alkali catalyst, and drying the obtained wet gel by a supercritical carbon dioxide drying method A manufacturing method comprising:
The silane-based surface treatment agent is represented by a chemical formula of Si (OCH 3 ) n X 4-n (n = 2 to 3, X = alkyl group), and tetraalkoxysilane / silane in a molar ratio. The manufacturing method of the nanostructure porous body excellent in hydrophobicity characterized by adding in the range of system surface treating agent = 9/1-2/8.
2. The method for producing a nanostructured porous body having excellent hydrophobicity according to claim 1, wherein ultrasonic synthesis is performed when a wet gel is synthesized by a sol-gel method.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05295117A (en) * | 1992-04-23 | 1993-11-09 | Matsushita Electric Works Ltd | Production of aerogel |
| JP2007099540A (en) * | 2005-09-30 | 2007-04-19 | Kobe Steel Ltd | Porous substrate and manufacturing method thereof |
-
2011
- 2011-09-12 JP JP2011197776A patent/JP2013060309A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05295117A (en) * | 1992-04-23 | 1993-11-09 | Matsushita Electric Works Ltd | Production of aerogel |
| JP2007099540A (en) * | 2005-09-30 | 2007-04-19 | Kobe Steel Ltd | Porous substrate and manufacturing method thereof |
Non-Patent Citations (3)
| Title |
|---|
| JPN6015014988; ＤＥ ＬＡ ＲＯＳＡ-ＦＯＸ，Ｎ． ｅｔ ａｌ: '"ＳＴＲＵＣＴＵＲＡＬ ＳＴＵＤＹ ＯＦ ＳＩＬＩＣＡ ＳＯＮＯＧＥＬＳ"' Ｊｏｕｒｎａｌ ｏｆ Ｎｏｎ-Ｃｒｙｓｔａｌｌｉｎｅ Ｓｏｌｉｄｓ Ｖｏｌ．１２１, 1990, ｐｐ．２１１-２１５ * |
| JPN6015014990; ＤＯＮＡＴＴＩ，Ｄ．Ａ． ｅｔ ａｌ: '"Ｆｒｏｍ ｓｏｌ ｔｏ ａｅｒｏｇｅｌ： Ａ ｓｔｕｄｙ ｏｆ ｔｈｅ ｎａｎｏｓｔｒｕｃｔｕｒａｌ ｃｈａｒａｃｔｅｒｉｓｔｉｃｓ ｏｆ ＴＥＯＳ ｄｅｒｉｖｅｄ ｓｏｎｏｇｅｌｓ"' Ｊｏｕｒｎａｌ ｏｆ Ｎｏｎ-Ｃｒｙｓｔａｌｌｉｎｅ Ｓｏｌｉｄｓ Ｖｏｌ．２９２, 2001, ｐｐ．４４-４９ * |
| JPN6015014991; ＶＯＬＬＥＴ，Ｄ．Ｒ． ｅｔ ａｌ: '"Ｍａｓｓ ｆｒａｃｔａｌ ｃｈａｒａｃｔｅｒｉｓｔｉｃｓ ｏｆ ｓｏｎｏｇｅｌｓ ｐｒｅｐａｒｅｄ ｆｒｏｍ ｓｏｎｏｈｙｄｒｏｌｙｓｉｓ ｏｆ ｔｅｔｒａｅｔｈｏｘｙｓｉｌａｎｅ ｗｉｔｈ ａｄｄ' Ｊｏｕｒｎａｌ ｏｆ Ｎｏｎ-Ｃｒｙｓｔａｌｌｉｎｅ Ｓｏｌｉｄｓ Ｖｏｌ．３５３, 20061109, ｐｐ．１４３-１５０ * |
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